10.
1 REACTION RATE
(a)
(b)
(c)
(d)
(a) Explain the effect of the following
factors on the reaction rate
i. [ ] & press ure
ii. Temperature
iii. Catalyst
iv. Particle size
(b) Explain the effect of temperature
on reaction rate using Maxwell-
Boltzmann distribution curve
REACTION KINETICS
(c) Explain the effect of catalyst on
activation energy using an energy
profile diagram
(d) State Arhenius equation
(e) Relate temperature & activation
energy to the rate constant based
10.3 FACTORS AFFECTING
on the Arhenius equation
REACTION RATE
(f) Determine k, Ea, T & A using
Arhenius equation by calculation &
graphical method
Explain collision theory
Define activation energy
Explain transition state theory
Draw energy profile diagram
of a reaction
(a) Define reaction rate
(b) Explain the graph of [ ] vs time in
relation to reaction rate
10.2 COLLISION (c) Write differential rate equation
THEORY & aA + bB cC
TRANSITION STATE Differential rate equation:
THEORY
(d) Determine rxn rate based on
differential rate equation
(e) define;
i. rate law
ii. Order of rxn
iii. Half life, t
(f)Write rate law with respect to the order
of reaction
(g) Write the integrated rate equation for
zero, 1st & 2dn order rxn
(h) Determine the order of reaction
involving a single reactant using
i. initial rate method
ii. The units of rate constants, k
iii. life based on the graph of [ ] vs
time
iv. Linear graph method based on the
integrated rate equation & rate law
(i) Perform calculations using integrated
rate equation
CHAPTER 10
REACTION KINETICS
 INTRODUCTION

Chemical kinetics is the study of

the rates of chemical reactions, the
factors that affect these rates, and
the reaction mechanisms by which
reactions occur.
 The study of reaction kinetics
Important

industrial process
-Time
-Optimum yield
-Optimum conditions
control over reaction,
obtain products economically
Objectives:

1. Define reaction rate

2. Explain the graph of concentration against
time in relation to reaction rate.
3. Write differential rate equation.
aA + bB cC
Differential rate equation:

4. Determine the reaction rate based on a

differential equation.
11.1 : Reaction rate
Reaction rate (R):

change in the concentration of a reactant or

product with time (M/s @ mol L-1 s-1).
1
rate
Time
 A B

time

During the reaction, reactant molecules (A) are

consumed while product molecules (B) are formed.

concentration of the reactant decreases while

concentration of the product increases.
 A B
[B]

[A]

[A] [A] = change in concentration of A over

rate = -
t time period t
[B] [B] = change in concentration of B over
rate =
t time period t
Because [A] decreases with time, [A] is negative.
 The average rate is the rate over a period of time.

A reaction rate calculated at a specified time is

known as Instantaneous rate.

The instantaneous rate at the beginning of a

reaction is called the initial rate of reaction.

Instantaneous rate :
determined from a graph of time versus
concentration by drawing a line tangent to the curve
at the point that corresponds to a particular time
 Rate of reaction
Reaction:
H2O2(aq) H2O(l) + O2(g)
Reaction rates are obtained
from the slopes of the
straight lines;
purple
An average rate form the
purple line.
The instantaneous rate at
blue red
t =300 s form the red line.
The initial rate form the
blue line.
 Example
Br2(aq) + HCOOH(aq) 2Br -(aq)+ 2H+(aq) + CO2(g)
The instantaneous rate of the above reaction at t =
100s, 200s and 300s are given by the slope of the
tangents at these times
 The differential rate equation
For stoichiometrically simple reaction such as

A B

Rate = - d[A] = d[B]

dt dt

The minus sign indicates concentration of A

decreases.
Unit: molL 1s 1
 For reactions, 2A B

2 of moles of A disappear for each mole of B

that forms.The rate of disappearance of A is
twice as fast as the rate of appearance of B

Rate = - 1 d[A] = d[B]

2 dt dt
 aA + bB cC + dD

rate = -
1 d[A] 1 d[B] 1 d[C] 1 d[D]
dt =- = =
a b dt c dt d dt
Write the rate expression for the following reaction:

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (g)

d[CH4] 1 d[O2] d[CO2] 1 d[H2O]

rate = - =- = =
dt 2 dt dt 2 dt
 Example 1
The formation of NH3,

N2(g) + 3H2(g) 2NH3(g)

The differential rate equation is;

d[N 2 ] 1 d[H 2 ] 1 d[NH 3 ]
Rate =
dt 3 dt 2 dt
The equation means that the rate of disappearance
of N2 is 1/3 the rate of disappearance of H2 and 1/2
the rate of formation of NH3.
Example 2
Consider the reaction, 2HI H2 + I2,
determine the rate of disappearance of HI when
the rate of I2 formation is 1.8 x 10-6 M s-1.
Solution
1 d[HI] d[H 2 ] d[I 2 ]
Rate =
2 dt dt dt
d[I 2 ]
= 1.8 10-6
dt
1 d[HI] d[I 2 ]
Rate =
2 dt dt
d[HI] = 2 1.8 10-6 = 3.6 10-6 M s-1
dt
Exercise 1:
Hydrogen gas produced nonpolluting product is
water vapour when react in O2 due to this reaction
has been used for fuel aboard the space shuttle,
and may be used by Earth-bound engines in the
near future.
2H2(g) + O2(g) 2H2O(g)

Express the rate in terms of changes in [H2],

[O2] and [H2O] with time.

When [O2] is decreasing at 0.23 mol L-1 s-1, at

what rate is [H2O] increasing?
(0.46 mol L-1 s-1)
 Exercise 2:
Consider the reaction,
NO(g) + O2(g) 2NO2(g).
Suppose that at a particular time during the
reaction nitric oxide (NO) is reacting at the rate of
0.066 M s-1

a) At what rate is NO2 being formed? (0.132 Ms-1)

b) At what rate is molecular oxygen reacting?
(0.066 M s-1 )
Exercise 3:

Consider the reaction,

N2(g) + 3H2(g) 2NH3(g)
Suppose that at a particular moment during the
reaction molecular hydrogen is reacting at the rate
of 0.074 M s-1

a) At what rate is ammonia being formed? (0.04933 M s ) -1

b) At what rate is molecular nitrogen reacting?

(0.02467 M s-1 )
 PSPM SK027 07/08

6(a) The reaction between gaseous ammonia

and oxygen is,

4NH3 (g) + 3O2 (g) 2N2 (g) + 6H2O (g)

Write the differential rate equation for the

reaction. If the rate of formation of water at a
given temperature and at a certain time is 0.81
M s-1 , determine the rate of disappearance of
ammonia. (5 marks)
 Objectives
At the end of the lesson the students should be able
to:
1. Define rate law, order of reaction and half life.
2. Write the integrated rate equation for zero, first and
second order reaction.
3. Write the integrated rate equation for zero, first and
second order reactions.
4. Perform calculations using the integrated rate
equations.
 Rate law / rate equation

An expression relating the rate of a reaction

to the rate constant and the concentrations of
the reactants raised to some powers.

At constant temperature and pressure,

R [reactants]
For a general reaction of the type,
aA + bB cC + dD

the rate law takes the form R [A]x[B]y

rate = k [A]x[B]y

[A] = concentration of A in molar

[B] = concentration of B in molar
k = rate constant
x = order with respect to A
y = order with respect to B
x + y = reaction order
 Order of reaction
The sum of the powers to which all reactant
concentrations appearing in the rate law are
raised.
The value of x and y must be determined
experimentally
Half-life , t
length of time required for the concentration
of a reactant to decrease to half of its initial
value.
 The units of rate constant, k
A Products
Rate, r = k [A]x

Rate = k [A] 0
i) Zero order
Rate = k
unit k = unit rate
= mol L-1 s-1 or M s-1
 rate
ii) First order Rate = k [A]1k=
[A]
M s -1
Unit k =
M
= s-1
Rate = k [A] 2
iii) Second order
rate
k=
[A]2
M s-1
Unit k = 2 = M-1 s-1
M
Example
S2O82- + 3I- 2SO42- + I3-
The above reaction is first order with respect to
iodide ions and to thiosulphate ions.
a) Write the rate of equation for the reaction.
b) What is the unit of rate constant, k?
Solution
a) Rate = k [S2O82-]1[I-]1
b) Rate = k [S2O82-]1[I-]1

k= rate Ms-1
[S2O82-]1[I-]1 Unit k = = M-1 s-1
M2
Rate Law
The values of x and y can only be determined
experimentally.
Reaction order is usually defined in term of
reactant concentrations.
The order of a reactant is NOT related to the
stoichiometric coefficients of the reactants in the
balanced chemical equation.

F2 (g) + 2ClO2 (g) 2FClO2 (g)

1
rate = k [F2][ClO2]
 Experimental Determination of Rate Law
For reaction : A B

rate = k[A]x
(i)For a certain reaction x = 0, the rate law for the
reaction is,
rate = k [A]0
rate = k
Rate of reaction is always constant.
This reaction is zero order with respect to A.
(ii) For a certain reaction where x = 1, the rate law for
the reaction is,
rate = k [A]1
Assume that initially [A] = 1.0 M .
rate1 = k (1.0 M)

Double the concentration of A from 1.0 M to 2.0 M

rate2 = k (2.0 M)
= 2k (1.0 M)
hence rate2 = 2 rate1

Thus, doubling the concentration of A will double the

rate of reaction.
this reaction is first order with respect to A.
(iii) For a certain reaction x = 2, the rate law for the
reaction is,
rate = k [A]2
Assume that initially [A] = 1.0 M .
rate1 = k (1.0 M)2
= k (1.0 M) 2
Double the concentration of A from 1.0 M to 2.0 M
rate2 = k (2.0 M)2
= 4k(1.0 M)
hence rate2 = 4 rate1

Doubling the concentration, the rate will increase by a

factor of 4.
This reaction is second order with respect to A.
 Determine the rate law and calculate the rate constant for
the following reaction from the following data:
S2O82- (aq) + 3I- (aq) 2SO42- (aq) + I3- (aq)
Initial Rate
Experiment [S2O82-] [I-]
(M/s)
rate = k [S2O82-]x[I-]y
1 0.08 0.034 2.2 x 10-4
y=1
2 0.08 0.017 1.1 x 10-4
x=1
3 0.16 0.017 2.2 x 10-4 rate = k [S2O82-][I-]
Double [I-], rate doubles (experiment 1 & 2)
Double [S2O82-], rate doubles (experiment 2 & 3)

rate 2.2 x 10-4 M/s

k= 2- - = = 0.08/Ms
[S2O8 ][I ] (0.08 M)(0.034 M)
 Example
Determining Reaction Order from Rate Law
For each of the following reactions, determine the
reaction order with respect to each reactant and the
overall order from the given rate law.

(a) 2NO(g) + O2(g) 2NO2(g); rate = k[NO]2[O2]

The reaction order respect to NO : 2

The reaction order respect to O2 : 1
overall reaction order = 3
(b) CH3CHO (g) CH4(g) + CO(g);
rate = k[CH3CHO]3/2

The reaction order with respect to CH3CHO : 3/2

The reaction order (overall) : 3/2

(c) H2O2(aq) + 3I-(aq) + 2H+(aq) I3-(aq)+ 2H2O(l);

rate = k[H2O2][I-]

The reaction of order with respect to H2O2 : 1

The reaction of order with respect to I- : 1
and zero order in H+, while overall order is 2.
 Integrated rate laws
Zero-order reaction
First-order reaction
Second-order reaction
*** Derivation of the integrated rate equation is not required.
ZERO ORDER REACTION
 Zero Order Reaction
zero order reaction is a reaction independent
of the concentration of reactant.
A product
The rate law is given by
rate = k[A]0
rate = k
Unit of k for zero order reaction Ms-1
 [ A]
-d =k
dt
Using calculus, -d[A] = k dt
- d[A] = k dt
- [A] = kt + c
Substituting t = 0, [A] = [A]0
- [A]0 = k (0) + c
c = - [A]0
[A]0 [A] = kt k = Ms-1
 Zero-Order Reactions
A product rate = k [A]0 = k

[A] = [A]0 - kt
[A] is the concentration of A at any time t
[A]0 is the concentration of A at time t=0
[ A]0
t = t when [A] =
2
[ A]0
[A]0 - = k t
2
[ A]0
t =
2k
Characteristic graph for zero order reaction

Rate

Zero Order

[A]

Graph of Rate versus [A]

Graph of [A]0-[A] versus t

[A]o[A]

T
Graph of [A] versus t
Half-life for zero-order reaction
FIRST ORDER REACTION
 First Order Reactions

first order reaction is a reaction which rate

depends on the concentration of reactant raised to
the first power.

From the rate law rate = k[A]

To obtain the units of k
k = rate/[A]
= M s-1/M

= s-1
 [ A] d [ A]
-d = k [A] = k dt
dt [ A]
using calculus
d [ A]
= kdt
[ A]

ln [A] = kt + c
substituting t = 0, [A] = [A]o

- ln [A]o = k(0) + c
c = ln[A]o
ln [A] = kt ln[A]o
ln[A] + ln [A]o = kt

ln [A ] 0 = kt
[A]

or when expressed in common logarithm

[A] 0 kt
log =
[A] 2.303
 Half life of a first order reaction
[A] 0
Substituting t = t , and [A] = into the first
order reaction, gives 2
[A] 0
ln = kt
[A]
[ A]0
ln [ A] = k t
0
2
ln 2 0.693
ln 2 = k t t = =
k k
 Characteristic graph for first order
i) Graph of Rate versus [A] ii) Graph of [A] versus t

Rate
[A]

[A] t
 First-order reaction
A product

t1=t2=t3=t4

t
t1 t2 t3 t4
iii) Graph of ln [A] versus t [A]o
iv) Graph of ln versus t
[A]

ln[A]
ln[A]o/[A]

ln[A]o

t
t
ln([A]o/[A]) = kt
ln[A]o ln[A] = kt
ln([A]o/[A]) = kt
ln[A] = kt + ln[A]o
y = mx
y = mx + c
 Example 1
The reaction 2A B is first order in A with a rate
constant of 2.8 x 10-2 s-1 at 800C. How long will it take for A
to decrease from 0.88 M to 0.14 M ?

[A]0 = 0.88 M
ln[A] = ln[A]0 - kt
[A] = 0.14 M
kt = ln[A]0 ln[A]
[A]0 0.88 M
ln ln
ln[A]0 ln[A] [A] 0.14 M
t= = = = 66 s
k k 2.8 x 10-2 s-1
 Example 2
What is the half-life of N2O5 if it decomposes with a rate
constant of 5.7 x 10-4 s-1?

t = ln2 =
0.693 = 1200 s = 20 minutes
k -4
5.7 x 10 s -1

How do you know decomposition is first order?

units of k (s-1)
 Example 3

For the first order decomposition of H2O2 (aq)

given the k = 3.66 x 10-3 s-1 and [H2O2]o=
0.882M, determine

a) the time at which [H2O2] = 0.600 M

b) the [H2O2] after 225 s.
Solution
a)
ln [H2O2]o = kt
[H2O2]

ln 0.882 = 3.66 x 103 s-1 x t

0.600

ln 1.47 = 3.66 x 103 s-1 x t

t = ln 1.47
3.66 x 103
= 0.385
3.66 x 103

= 105.263s
b) ln [H2O2]o = kt
[H2O2]

ln 0.882 = 3.66 x 103 s-1 x 225 s

[H2O2]
= 0.824

0.882 = e0.824
[H2O2]

0.882 = 2.280
[H2O2]o

[H2O2] = 0.882 =0.387 M

2.280
 Example 4
The decomposition of ethane C2H6 to methyl
radicals is a first order reaction with a rate
constant of 5.36 x 10-4s-1 at 700oC.
C2H6 (g) 2CH3 (g)
Calculate the half life of the reaction in minutes.
Solution
t = ln 2
k
= 0.693
5.36 x 10-4
= 1.29 x 103 s
= 21.5 min
SECOND ORDER REACTION
 Second Order Reactions

A second order reaction is a reaction which rate

depends on the concentration of one reactant raised
to the second power or on the concentration of two
different reactants each raised to the first power.

The simpler type involves only one type of reactant

molecule.

A product
Where d[A]
rate = = k[A]2
dt
From the rate law , rate = k[A]2

As before, we can determine the units of k by

writing
k = rate
[A]2

= M-1s-1

Using calculus we obtain the following expression

1 = 1 + kt
[A] [A]0
 Half life of a second order reaction
Substituting t = t , and [A] = [A]o
2
into the second order reaction, gives
1 = 1 + kt
[A] [A]0

1 = 1 + kt
[A]0 [A]o

t = 1
k[A]o
Characteristic graph for second order
reaction
Rate

[A]

Graph of Rate versus [A]

C
 1
Graph of versus t
[ A]
1
[ A]

t
Half-life for second-order reaction
 Example
Iodine atoms combine to form molecular iodine in
the gas phase.
I(g) + I(g) I2(g)
This reaction follows second order and has a high
rate constant 7.0 x 109 M-1s-1.

i) If the initial concentration of iodine was 0.086

M, calculate the concentration after 2 min.

ii) Calculate the half life of the reaction if the initial

concentration of iodine is 0.06 M and 0.42 M
respectively.
 Solution
i) 1 = 1 + kt
[A] [A]o
1 = 1 + (7.0 x 109 M-1s-1)(2x60)
[A] [0.886]
= 1.1287 + (8.4 x 1011)
= 8.4 x 1011
[A] = 1.190 x 10-12 M
ii) [I2]0 = 0.06 M
t = 1
k[A]o
= 1
(7.0 x 109 M-1s-1)(0.60M)
= 2.4 x 10-10s

[I2] = 0.42 M
t = 1
k[A]o
= 1
(7.0 x 109 M-1s-1)(0.042M)
= 3.4 x 10-10 s
Summary of the Kinetics of Zero-Order, First-Order
and Second-Order Reactions

Concentration-Time
Order Rate Law Equation Half-Life
[A]0
0 rate = k [A] = [A]0 - kt t =
2k

1 rate = k [A] ln[A] = ln[A]0 - kt t = ln2

k
1 1 1
2 rate = k [A]2 = + kt t =
[A] [A]0 k[A]0
 PSPM SK027 10/11
6 (b) TABLE 4 shows initial rate for the reaction:

- - -
2MnO4 + 5CIO3 6H+ 2Mn2+ + 5CIO4 + 3H2O

Determine the rate law and the rate constant for the reaction.
TABLE 4
- +
Experiment [ MnO4] / M [CIO3 ] / M [H ] / M Initial rate
-1
(Ms )
-3
1 0.10 0.10 0.10 5.3 x 10
-2
2 0.25 0.10 0.10 3.3 x 10
-2
3 0.10 0.30 0.10 1.6 x 10
-3
4 0.10 0.10 0.20 7.4 x 10
[8 marks]
 Objective
At the end of the lesson the students should be
able to:

1.Determine the order of reaction involving a single

reactant using:
i) initial rate method
ii) the units of rate constants, k
iii) Half-life based on the graph concentration
against time.
iv) linear graph method based on the integrated
rate equation and rate law.
 Determination the order of a reaction

1) The initial rate method

Compare the initial rate at difference
concentration

x y
rate1 k[ A1 ] [ B1 ]
x y
rate2 k[ A2 ] [ B2 ]
Example

[ ] mol dm-3 Initial Rate

Exp [M] [N] (Ms-1)
1 0.50 1.0 2.0
2 0.50 2.0 8.0
3 0.50 3.0 18.0
4 1.0 3.0 18.0

a) Determine the order of the reaction

b) Write the rate law
 Solution
To determine the order with respect to M
From exp. 3 & 4 ( where [ N ] constant )
x y
rate1 k[ M 1 ] [ N1 ]
x y
rate2 k[ M 2 ] [ N 2 ]
x y
18.0 k 0.50 3.0
x y
18.0 k 1.0 3.0
x=0

Zero-order with respect to M

 To determine the order with respect to N
From exp 1 & 2 ( where [ M ] constant )
x y
rate1 k[ M 1 ] [ N1 ]
x y
rate2 k[ M 2 ] [ N 2 ]
x y
2.0 k[0.5] [1.0]
x y
8.0 k[0.5] [2.0]
n=2
Second-order with respect to N

b ) Rate law, rate = k [ N ]2

 Determination of the orders of reaction rate;
O2(g) + 2NO(g) 2NO2(g)

Initial Reactant
Concentrations (molL-1)
Exp O2 NO Initial Rate (Ms-1)
1 1.10x10-2 1.30x10-2 3.21x10-3
2 2.20x10-2 1.30x10-2 6.40x10-3
3 1.10x10-2 2.60x10-2 12.8x10-3
4 3.30x10-2 1.30x10-2 9.60x10-3
5 1.10x10-2 3.90x10-2 28.8x10-3
 Solution
O2(g) + 2NO(g) 2NO2(g)
rate = k [O2]m[NO]n
Compare 2 exp in which the [ ] of one reactant varies
and the [ ] of the other reactant(s) remains constant.
rate2 k [O2]2m[NO]2n [O2]2m [O2]2 m
= = =
rate1 k [O2]1m[NO]1n [O2]1m [O2]1

6.40x10-3Ms-1 = 2.20x10-2mol/L m
3.21x10-3Ms-1 1.10x10-2mol/L
2 = 2m ,m=1

The reaction is first order with respect to O2

The order with respect to NO, compare exp 3 and 1,
in which [O2] is held constant and [NO] is doubled:
n
Rate 3 k [O2]3m [NO]3n [NO]3
= =
Rate 1 k [O2]1m [NO]1n [NO]1

n
12.8 x10-3Ms-1 2.60 x 10-2mol/L
-3 -1
=
3.21 x 10 Ms 1.30 x 10-2mol/L
n
4=2 ; n=2
The reaction is second order with respect to NO
Thus the rate law is :
Rate = k[O2][NO]2
Exercise
ClO2(aq) + 2OH- (aq) products
The results of the kinetic studies are given below.
exp [ClO2] [OH-] Initial rate,
M M Ms-1
1 0.0421 0.0185 8.21 1 0-3
2 0.0522 0.0185 1.26 1 0-2
3 0.0421 0.0285 1.26 1 0-2

a) Explain what is meant by the order of reaction.

b) Referring to the data determine
(i) rate law /rate equation
(ii) rate constant, k
(iii) the reaction rate if [ClO2] and [OH-] = 0.05 M
Exercise

Write rate law for this equation,

A + B C
i) When [A] is doubled, rate also doubles. But
doubling the [B] has no effect on rate.
ii) When [A] is increased 3x, rate increases 3x,
and increasing of [B] 3x causes the rate to
increase 9x.
iii) Reducing [A] by half has no effect on the rate,
but reducing [B] by half causes the rate to be
half the value of the initial rate.
 Exercise
Many gaseous reactions occur in a car engine and
exhaust system. One of the gas reaction is given
below.
NO2(g) + CO(g) NO(g) + CO2(g)
Rate = k [NO2]m[CO]n
Use the following data to determine the individual and
overall reaction orders:
Exp Initial Rate(Ms-1) Initial [NO2](M) Initial [CO](M)
1 0.0050 0.10 0.10
2 0.080 0.40 0.10
3 0.0050 0.10 0.20
2 ) From the unit of rate constant, k
For zero order reaction, rate = k
Unit for rate constant, k = mol L-1 s-1 or M s-1

For first order reaction, rate = k [A]

Unit for rate constant, k = s-1

For second order reaction, rate = k [A]2

Unit for rate constant, k = M-1 s-1
3) Graphical method
a) Half-life method
Plot the graph [ ] versus t
Zero-order reaction

[ A]
k
2t 1
2
 0.693 1
k k
t1 [ A]0 t 1
2 2
b ) linear graph method based on integrated
rate equation
Zero-order reaction
Plot the graph [ ] versus time
[ ]
[A] = - kt + [A]0

y = mx + c

t
First-order reaction Second-order reaction
1
Graph of ln [A] versus t Graph of versus t
1 [ A]
ln [A]
[ A]

t t
1 1
kt
ln [A] - kt ln [A] 0 [ A] [A] 0
 Exercise
For the reaction:
4NH3 (g) + 5O2 (g) 4NO(g) + 6H2O (l)
Oxygen gas is reacting at the rate 0.72 Ms-1.
a) Write the differential rate equation.
b) Calculate the rate of
i ) water formation
ii ) ammonia consumption
 PSPM SK027 07/08
6(b) A gas R dissociates into gases S & T according to
the equation,
R(g) S (g) +T (g)
The data for the dissociation are given in TABLE 1.
t/min Px/atm By plotting an
0 1.00 appropriate graph,
20 0.63 show that the
40 0.41 reaction is first order.
60 0.27 Determine the rate
80 0.16 constant and the half
100 0.10 life of the reaction.
(10 marks)
 10.2 The Collision Theory
Objectives
At the end of the lesson the students should
be able to:
1. Explain collision theory.

2. Define activation energy.

3. Explain transition state theory.

3. Draw energy profile diagram of a

reaction.
 10.2 The Collision Theory
Chemical reactions occur as a result of
collision between reacting molecules.
The rate of a reaction is directly
proportional to the number of collisions
per second.
rate number of collision
s

video
 10.2 The Collision Theory

The collision theory states that for a chemical

reaction to occur, the reacting particles must:
(a) collide with each other so that the breaking
and formation of chemical bonds can occur.
(b) possess energy that is equal to or more than
the minimum energy called the activation
energy.
(c) collide in the correct orientation.
 10.2 The Collision Theory
Collisions that result in the formation of
products are called EFFECTIVE
COLLISIONS.
Effective collisions:
Molecules must have total potential
energy equal to or greater than the
activation energy (Ea)
Molecules must collide at correct
orientation.
Activation energy (Ea) is the
minimum amount of energy required to
initiate a chemical reaction.
 Reaction Energy Profile
A reaction profile shows potential energy plotted
as a function of the progress of the reaction for
the reaction:
A +BC AB +C.
As the reaction
progresses,
kinetic energy of
the reactants is
first converted
into potential
H
energy of the
transition state
and is then
transformed into
kinetic energy of
 The Transition State Theory
The configuration of the atoms of the colliding
species at the time of the collision is called the
transition state.

The transitional structure/ temporarily

spesies formed by the reactant molecule
results from an effective collision that
persists while old bonds are breaking and
new bonds are forming before they form the
product is called, the activated complex.
 Reaction Energy Profile
The difference in
The profile is drawn for an potential energies
exothermic reaction: between the
products and the
reactants is H for
the reaction.

Reactant
molecules must
H
have enough
energy to
overcome an
energy barrier
separating
products from
 Example:
Activated complex
Transition state

Ea (Forward reaction)
Ea (reverse
reaction)

CO(g) + NO2(g) CO2(g) +

 Reaction Energy Profile for
Endothermic Reaction

Ea
(reverse reaction)
Ea
(forward reaction)

H
 Example:

Ea

2NOCl 2NO + Cl2

 Characteristic of Activated Complex
Very unstable i.e. It has a short
half-life.
Its potential energy is greater than
reactants or products.
The activated complex and the
reactants are in chemical
equilibrium.
It decomposes to form products or
reactants.
Example:
1. For the reaction A + B C + D , the enthalpy
change of the forward reaction is + 21 kJ/mol. The
activation energy of the forward reaction is 84 kJ/mol.
a) What is activation energy of the reverse reaction?
b) Sketch the reaction profile of this reaction

2. Draw a potential energy diagram for an exothermic

reaction. Indicate on the drawing:
a) Potential energy of the reactants and the products
b) The activation energy for the forward and the reverse
reaction
c) The heat of the reaction
 10.2 The Collision Theory
In order to make the H
CH3I molecule, the I
I C Br
must bond with the
C, so it must collide H

with the C. If it hits

the Br, then a
reaction will NOT H
occur.
C Br I
Picture (a) shows
H
correct orientation
while (b) does not.
 Orientation Factor
We must also consider the orientation factor, that is how
the reacting molecules are oriented relative to each other.

This reaction is most favorable only when the K atom

collides with the I atom in CH3I head-on. Otherwise, few or
no products are formed.
10.3 Factors Affecting Rate of Reactions
Objectives
At the end of the lesson the students should
be able to:
1. Explain reaction rates in terms of
collision theory.
2. Identify factors affecting the
effectiveness of collision.
3. Define activation energy.
4. Define and state the characteristics of
an activated complex
 Medications

Why do you think

that certain pills are
found as small
spheres of the
medication inside a
soluble capsule?
 Medications

The more surface

area the
medication has, the
faster it will react.
These small
spheres allows
more surface area
and a faster
reaction.
 Why do we refrigerator our foods in terms
of the collision theory?

If we lower the
temperature of the
food, then the decay
reactions will slow
down. The colder the
molecules are, the less
energy they have to
collide and thus the
less effective collisions
 Dangerous Habit
What is especially
dangerous about this
smoking situation?
The man has an
oxygen mask (30%)
over his nose and
mouth. Describe the
dangers in terms of
the collision theory.
 Dangerous Habit
The man is breathing
in more concentrated
oxygen. Since
oxygen is needed for
combustion,
combustion will
proceed faster with a
higher concentration
of O2. This could
cause a serious fire
with the lit cigarette.
Factors Affecting Rate of Reactions
1. Nature of the reactants complexity of
the molecules; states of matter
2. surface area
3. temperature
4. concentration
5. catalysts
 Effect of concentration on the rate of
reaction
Change in the [ ] of reactants change the number
of particles per unit volume and increase the
number of collisions per unit time in that volume.

If [ ] is doubled the number of collisions would

also doubled, because in any given volume there
would be twice as many molecules that could
collide.

Consequently the rate would increase by a factor

of 2.
 According to the collision theory, an
increase in the number of collisions will
bring an increase in the rate of reaction.

Number of molecular collisions is

proportional to the concentration.
 Example:

Magnesium reacts with dilute hydrochloric

acid according to the equation:
Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
When the concentration of hydrochloric
acid increases, the rate of reaction also
increases.
 When the concentration of hydrochloric acid
increases, the number of particles per unit
volume also increases and the particles are
closer together.

Same
volume

When the number of particles increases, the

frequency of collisions also increases. As a
result, the frequency of effective collisions
increases. This causes the rate of reaction to
Effect of pressure on the rate of reaction
 Effect of pressure on the rate of reaction

Example: N2(g) + O2(g) 2NO(g)

The rate of reaction between nitrogen and
oxygen to produce nitrogen monoxide can
be increased by increasing the pressure.

Number of particles
same
At high pressures,
the number of gaseous molecules per unit volume
is increased and the gaseous molecules are
packed closer together.
causes the gaseous molecules to collide more
frequently.
Consequently, the frequency of effective
collisions increases and the rate of reaction also
increases.

Number of particles
same
Effect of temperature on the rate of reaction
The higher the temperature the higher the rate
of reaction
Example: Calcium carbonate reacts with
hydrochloric acid to form carbon dioxide
according to the following equation:
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) +
CO2(g)
 When the temperature is increased, the
particles absorb the heat energy. As a result,
the kinetic energy of the particles
increases. Hence,
(a) the reacting particles move faster, and
(b) the number of reacting particles with the
activation energy required increases.
Consequently, the frequency of effective
collisions increases and hence, the rate of
reaction also increases.
Kinetic energy distributions for a reaction mixture at
two different temperatures.

Ea
Maxwell-Boltzmann speed distribution for a gas at
temperature T1 and temperature T2,
 Maxwell-Boltzmann distribution defines the
distribution of the different kinetic energies of
particles in a system.

Note that the curve flatten at the higher

temperature.

The shaded areas represent the number of

molecules traveling at a speed equal to or greater
than activation energy, Ea.
 The higher the temperature, the greater
the number of molecules moving at high
speed.

Only fast-moving molecules have sufficient

kinetic energy to overcome the activation
energy.
 Effect of catalysts on reaction rates
A catalyst is substance that increases the rate of
a chemical reaction without itself being
consumed.
Increase the rate of a chemical reaction by
providing an alternative reaction pathway with a
lower activation energy.
 Effect of catalysts on reaction rates
Example: The decomposition of hydrogen
peroxide to water and oxygen occurs very slowly
at room temperature.
2H2O2(aq) 2H2O(l) +O2(g).
In the presence of a catalyst, the decomposition
of hydrogen peroxide occurs rapidly.
 A catalyst provides an alternative reaction route
(or pathway) for the reaction to occur.
An alternative route has a lower activation
energy.
As a result, more reacting particles possess
sufficient energy to overcome the lower
activation energy required for effective collisions.

Hence, the
frequency of
effective
collisions
increases and the
rate of reaction
increases
Addition of a catalyst increases the reaction
rate by increasing the frequency of effective
collision. That is by
Decreasing the Ea, and
Correct orientation

Example : surface-catalyzed
reaction

Adsorption of Diffusion of Formation of

reactants reactants along product
In a surface-catalyzed reaction, almost
all the catalysts surface is covered by
adsorbed molecules.
Molecules that are adsorbed on a surface
are thus closer to each other.
Its easier for the electron clouds of
these molecules to interact and bonds to
form or break.
The molecules need not possess a
minimum kinetic energy for an effective
collision to take place.
Comparison of the activation energy of the catalyzed
and uncatalyzed reactions
 Effect of surface area on the reaction rate
The smaller the size of reacting particles, the
greater is the total surface area exposed for
reaction and consequently the faster the
reaction.

In the case of heterogeneous systems, in which

the reactants are in different phases, the area of
contact between the reacting substances will
influence the reaction rate
 Effect of surface area on the reaction rate
The sodium chloride crystal as shown in Figure (a) has a
surface area of 16 cm2. Surface area of the NaCl crystal
=(1 x 2) x 4 + (2 x 2) x 2 =16cm2
When this crystal is divided into smaller crystals as shown
in (b), the total surface area is increased to 24 cm2.
The greater the surface area of a solid, the higher the
reaction rate.
A greater area causes a greater frequency of collisions,
thus increasing the reaction rate.
 Example:
In the reaction between hydrochloric acid and marble chips
(calcium carbonate),
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)
The rate of reaction will increase if powdered marble is
used instead of marble chips.
 The total surface area is larger in powdered
marble.
With greater surface area exposed for reaction
with the acid collisions between reacting
molecules become more frequent.
This means that the frequency of effective
collisions (that is, collisions with the correct
orientation and with energy equal to or greater
than activation energy) between reacting
particles will increase.
As a result, the rate of reaction also increases.
Relating the frequency of effective collisions
with factors influencing the rate of reaction
According to the collision theory, two important
factors that determine the rate of a chemical
reaction are:
(a) the frequency of effective collisions and
(b) the magnitude of the activation energy

In general, any factor that increases

the rate of effective collisions will
also increase the rate of reaction.
Relating the frequency of effective collisions
with factors influencing the rate of reaction
1 Frequency of effective collisions
For a given reaction, if the frequency of
collisions between reactant molecules is high,
it follows that the frequency of effective
collisions that causes a reaction to occur will
also be high.
As a result, the rate of reaction increases.
 Relating the frequency of effective collisions
with factors influencing the rate of reaction
2 Magnitude of activation energy
Reactions that have high activation energy will
occur at a slow rate. This is because only a
small fraction of the molecules possess
sufficient energy to overcome the activation
energy for the reaction to occur.
 Relating the frequency of effective collisions
with factors influencing the rate of reaction
2 Magnitude of activation energy
In contrast, reactions that possess low
activation energy will occur at a fast rate.
This is because most of the molecules
have sufficient energy to overcome the
activation energy.
The frequency of effective collisions
that causes a reaction to occur will also
be high.
 The Arrhenius Equation

The dependence of the rate constant of a reaction on

temperature can be expressed by the following
equation known as Arrhenius equation.
Ea = activation energy
Ea k = rate constant
k=A e RT R = gas constant
T = absolute temperature
e = the base of the natural
logarithm scale
A = quantity represents the collision
frequency (frequency factor)
By taking the natural logarithm of both sides.
ln k = ln Ae -Ea/RT
ln k = ln A Ea/RT
The equation can take the form of a linear equation

ln k =(
Ea )(
1 ) + ln A
R T
y x c
m
1
A plot of ln k versus gives a straight line
T
Slope m =
Ea and intercept c with the y axis is ln A.
R
 The rate constants for decomposition of
Example
acetaldehyde
2HI(g) H2(g) + I2(g)
were measured at five different temperatures.
The data
are shown below. Plot ln k versus 1/T, and
determine
the activation energy (in kJ/mole) for the
reaction. k (1/M s) T (K)
3.52 x 10-7 283
3.02 x 10-5 356
2.19 x 10-4 393
1.16 x 10-3 427
3.95 x 10-2 508
 Solution
We need to plot ln k on the y-axis versus
1/T
on the x-axis. From the given data we
obtain ln k 1/T (K-1)
14.860 3.53 x 10-3
10.408 2.81 x 10-3
8.426 2.54 x 10-3
6.759 2.34 x 10-3
3.231 1.97 x 10-3
 ln k

-2

-4

-6

-8 y

-10

-12

-14
x
-16
x 10-3
1.0 2.0 3.0
1/T(K-1)

Plot of ln k versus 1/T. The slope of the line

is calculated from two pairs of coordinates.
 Slope = (-14.860) (-3.231) = -7454.5 K
(3.53-1.97) x 10-3 K-1

Finally, calculate the activation energy from the

slope:

The slope, m = Ea/R.

Ea = R (m)
= (8.314 J K-1 mol-1) (-7454.5 K)
= 61976.6 J mol-1
= 61.976 kJ mol-1
 An equation relating the rate constants k1 and k2 at
temperatures T1 and T2 can be used to calculate
the activation energy or to find the rate constant at
another temperature if the activation energy is
known.

Ea 1 Ea 1
ln k1 ( ) ln A and ln k 2 ( ) ln A
R T1 R T2

Rearranging the equations would give

Ea 1 Ea 1
ln k1 ( ) ln A ln k2 ( ) ln A
R T1 R T2
Since A is a constant
Ea 1 Ea 1
ln k1 ( ) ln k2 ( )
R T1 R T2

Ea 1 Ea 1
ln k1 ln k2 ( ) ( )
R T2 R T1

k1 Ea 1 1
ln ( )
k2 R T2 T1
 Example
The rate constant of a first-order reaction is 3.46 x
10-2s-1 at 298 K. What is the rate constant at 350
K if the activation energy for the reaction is 50.2
kJ/mole?
Solution
Given
k1 = 3.46 x 10-2 s-1 k2 = ?
T1 = 298 K T2 = 350 K

Substituting in equation
k1
ln = Ea 1 1
k2 R T2 T1
ln 3.46 x 10-2 = 50.2 x 103 J/mol 298K 350K
k2 8.314 J/K mol (298K)(350K)

Solving the equation gives

ln 3.46 x 10 -2 = 3.01
k2
3.46 x 10 -2 = 0.0493
k2
k2 = 0.702 s 1
Exercise: the Activation energy
The decomposition of hydrogen
iodide,
2 HI (g) H (g) + I (g)
2 2

has rate constants of 9.51 x 10-9 L

mol-1 s-1 at 500 K and 1.10x10-5 L
mol-1 s-1 at 600 K. Find Ea.

( Ea = 1.76 x 105 J/mol = 176

kJ/mol )
 Arrhenius Equation

The ratio of rate constant at 2

different temperatures
Conclusion : Factors affecting rate of reac
CONCENTRATIONS OR PRESSURE OF
REACTANTS:
Reaction rates generally increase as the
concentrations of the reactants are increased.
TEMPERATURE:
Reaction rates generally increase rapidly
as the temperature is increased.

CATALYSTS:
Catalysts speed up reactions.

PARTICLE SIZE:
The rate increases as the smaller the size
of reacting particles .
 change Effect of the Effect on the
rate of reaction rate constant
Increasing [ ] Increases No effect
Decreasing [ ] Decreases No effect
Increasing P Increases No effect
Decreasing P Decreases No effect
Increasing T Increases Increases
Decreasing T Decreases Decreases
Addition of catalyst Increases Increases